EP4003954A1 - Accélérateur en bande et son utilisation, matériau d'isolation solide et système d'isolation exempt d'anhydride - Google Patents

Accélérateur en bande et son utilisation, matériau d'isolation solide et système d'isolation exempt d'anhydride

Info

Publication number
EP4003954A1
EP4003954A1 EP20764002.0A EP20764002A EP4003954A1 EP 4003954 A1 EP4003954 A1 EP 4003954A1 EP 20764002 A EP20764002 A EP 20764002A EP 4003954 A1 EP4003954 A1 EP 4003954A1
Authority
EP
European Patent Office
Prior art keywords
accelerator
tape
anhydride
belt
sulfonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20764002.0A
Other languages
German (de)
English (en)
Inventor
Mario Brockschmidt
Jürgen Huber
Torsten Rossow
Dieter Schirm
Matthias ÜBLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Innomotics GmbH
Original Assignee
Siemens AG
Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of EP4003954A1 publication Critical patent/EP4003954A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/59—Arsenic- or antimony-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/446—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylacetals
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K3/00—Details of windings
    • H02K3/30—Windings characterised by the insulating material
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K3/00—Details of windings
    • H02K3/32—Windings characterised by the shape, form or construction of the insulation
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K2213/00—Specific aspects, not otherwise provided for and not covered by codes H02K2201/00 - H02K2211/00
    • H02K2213/03—Machines characterised by numerical values, ranges, mathematical expressions or similar information

Definitions

  • the invention relates to a belt accelerator and a fes th insulation material with this belt accelerator, as it can be used to produce an anhydride-free insulation system for motors and generators - for example in the form of a winding belt insulation.
  • the invention relates to an anhydride-free insulation system which can be produced by vacuum-pressure impregnation -VPI- process.
  • Such an insulation system comprises a solid insulation material, from which the anhydride-free insulation system is produced by impregnation and / or casting with an impregnating agent and subsequent curing.
  • Rotating electrical machines include an electrical winding within a laminated core, such as a stator winding.
  • the winding is made up of electrical conductors, which may already be provided with primary insulation, and solid insulation materials as the main insulation against the laminated core. Without further measures, there is no intimate connection between the laminated core, the conductors and the main insulation, so that gaps and cavities remain. Under atmospheric conditions, these areas would be filled with air. In the case of applications in the medium and / or high voltage range, such as motors and generators or large electrical drives, this is not permitted, as partial electrical discharges in the cavities and gaps would destroy the insulation in a very short time. A resulting electrical breakdown, for example, means the failure of the electrical machine.
  • this liquid resin component is called "impregnating agent" because, in addition to the actual resin component, the impregnating resin, it can also include hardeners, catalyst (s), thinners, additives, fillers, etc.
  • the impregnating agent can also include hardeners, catalyst (s), thinners, additives, fillers, etc.
  • Particularly suitable solid insulation materials are porous insulation materials such as mica tape, insulation paper, and / or nonwovens, as well as any combinations thereof.
  • windings made of solid insulation materials are the usual state of the art technology, which by means of a vacuum pressure impregnation process -VPI - with mixtures with liquid epoxy resins and liquid, cyclic acid anhydrides be impregnated in the impregnation agent.
  • the solid insulation material is a barrier material that is glued with a tape adhesive.
  • a tape adhesive Dissolved and / or finely distributed in it is the so-called “belt accelerator", which first initiates the gelation, i.e. the formation of the pre-hardened synthetic resin and then promotes complete hardening, provided that the polymerization of the liquid impregnation agent does not itself keep going.
  • the tape adhesive serves - for example - to connect mica paper and carrier materials such as foils and / or glass fabric, whereas the proportional tape accelerator causes the low-viscosity impregnating resin to gel to the hardened synthetic resin.
  • the liquid impregnating agent penetrating into the winding made of solid insulation material removes the belt accelerator from the solid insulation material and thus causes the belt accelerator to migrate and distribute in the impregnating agent. After gelation, the impregnated winding is thermally hardened in the manufacture of the finished anhydride-free insulation system.
  • the belt accelerator is provided as a depot in the solid insulation material, the impregnation never results in a completely homogeneous distribution of the belt accelerator in the impregnating agent. Rather, there are areas of high and low belt accelerator concentration.
  • the - in particular cyclic - acid anhydrides previously contained in the impregnation agent serve as hardeners for the epoxy groups and at the same time reduce the viscosity of the impregnation agent as a whole, which is beneficial for rapid and complete impregnation of the solid insulation material.
  • a mixture of distilled bisphenol A diglycidyl ether as the impregnating resin and a methylhexahydrophthalic anhydride as the anhydride-containing hardener has established itself as an impregnating agent as an impregnating agent, both together result in a very thin liquid formulation that, in the absence of a belt accelerator, can last for a long time Has storage stability at room temperature and also at impregnation temperature.
  • the preferred belt accelerator is a compound called zinc naphthenate, which is derived from petroleum.
  • other synthetic belt accelerators are known to the person skilled in the art, such as those from EP 0424376 Bl.
  • MHHPA Methylhexahydrophthalic anhydride
  • composition of the solid insulation material for example the mica tapes
  • the coordination of tape adhesive and tape accelerator must be redesigned for the use of anhydride-free impregnation agents.
  • these belt accelerators no longer show sufficient effectiveness from concentrations of approx. 1% by weight and less, so that even after the solid insulation material has been impregnated with the impregnation agent and gelation and subsequent hardening, there are still liquid and unpolymerized parts of the impregnating resin in a quantity that prevent a resilient insulation system with only a small number of imperfections such as air bubbles from forming.
  • Table 1 shows the enthalpy of reaction of long-known anionic belt accelerators, which react with an anhydride-free impregnating agent, but in catalytic amounts of 1% by weight or less, as is always found in areas with a low concentration of belt accelerator when potting There is isolation, react too weakly.
  • reaction enthalpy of -378 Jg _1 is sufficient for a stable insulation system, but a reaction enthalpy of - 8.3 Jg _1 is no longer.
  • the proportions of impregnating agent that has not yet polymerized can be measured via DSC - differential scanning calorimetry as incomplete curing via the reaction exotherm.
  • Figures 1 and 2 show the DSC measurements for Table 1.
  • the subject matter of the present invention is a cationic belt accelerator for use in a process for the production of an insulation system by impregnation and / or encapsulation with an anhydride-free impregnation agent, which is an ionically composed compound of one or more sulfonium-containing cation (s) with one or more hexafluoroantimonate anion (s).
  • anhydride-free impregnation agent which is an ionically composed compound of one or more sulfonium-containing cation (s) with one or more hexafluoroantimonate anion (s).
  • the subject of the present invention is a cationic belt accelerator for use in a process for the production of an insulation system by potting with an anhydride-free impregnating agent, the belt accelerator being a chemical compound that falls under one of the structural formulas I, II or III:
  • FIG. 3 shows the structural formula “Structure I” of a cationic belt accelerator according to a preferred embodiment of the present invention.
  • the invention also relates to the use of the belt accelerator for producing an anhydride-free insulation system by impregnating the solid insulation material with an impregnating agent, the impregnating agent comprising an aromatic and / or cyclo-aliphatic impregnating resin that is anhydride-free and epoxy groups. is relevant.
  • the subject matter of the invention as an independently tradable intermediate product comprises a solid insulation material, a barrier material, a tape adhesive and a tape accelerator, the tape accelerator being a cationic tape accelerator and an ionic compound of a sulfonium-containing cation with a hexafluoroantimontium anion , such as 4-acetyloxyphenyl-dimethylsulfonium-hexafluoroantimonate - CAS-No.135691 -31-5- structure I contains. Structure i
  • the subject of the invention is an insulation system, producible by casting a solid insulation material with a belt accelerator, which is an ionogenic compound composed of a sulfonium-containing cation with a hexafluoroantimonate anion, in particular a compound according to structural formula I with an anhydride -free impregnating agent, contains.
  • a compound according to structure I is in particular a compound available commercially under the name 4-acetyloxyphenyl-dimethylsulfonium-hexafluoroantimonate.
  • a solid insulation material which, as a cationic band accelerator, contains an ionogenic compound of a sulfonium-containing cation with a hexafluoroantimonate anion, in particular the compound of structural formula I at least in large part, with an anhydride -free impregnation resin, especially epoxy resin-based, also in areas with low belt accelerator concentrations, i.e.
  • a “cationic belt accelerator” is a belt accelerator which is ionogenic and whose cation in a liquid impregnant initiates the cationic polymerization, in particular the cationic homopolymerization of an impregnating resin.
  • Heteropolar compounds are referred to as "ionogenic” compounds, the chemical reactivity of which is characterized by the presence of a cation and an anion in the compound.
  • Classical "ionogenic” compounds are salts.
  • complex structures with a cationic and anionic character are also referred to here as “ionogenic” compounds.
  • a "sulfonium-containing cation” is a cation which, in addition to the anion or anions, comprises a unit in the molecule that can be described by the simply positively charged structures II or III or by the empirical formula [SRs] + .
  • Cationic structure II is a cation which, in addition to the anion or anions, comprises a unit in the molecule that can be described by the simply positively charged structures II or III or by the empirical formula [SRs] + .
  • alkyl-aryl-sulfonium or di-alkyl-aryl-sulfonium denotes a sulfonium-containing cation in which one or two of the three radicals “R” on the sulfur atom in the sulfonium cation are alkyl groups.
  • Alkyl groups are parts of a molecule that consist of carbon and hydrogen atoms connected to one another.
  • preferred alkyl radicals are those with 1 to 12 carbon atoms, which can be branched or linear.
  • the alkyl groups are monovalently linked to the central sulfur atom.
  • one or two alkyl radicals can be present in a di-alkyl-aryl-sulfonium cation, which in turn can be identical or different.
  • aryl-alkyl-sulfonium or di-aryl-alkyl-sulfonium denotes a sulfonium-containing cation in which one or two of the three radicals “R” on the sulfur atom in the sulfonium cation are aryl groups.
  • Aryl groups are parts of a molecule that are monovalent on the carbon structure or on the sulfur atom, and have at least one aromatic nucleus, which can be partially or completely - substituted or - unsubstituted.
  • one or two aryl radicals can be present in an aryl-alkyl-sulfonium cation, which in turn can be identical or different.
  • the third radical can be any, including an alkyl group or an aryl group, completely or partially substituted or not.
  • aryl group is an organic chemical radical with an aromatic backbone. It is the name for a monovalent group of atoms derived from aromatic hydrocarbons by removing a hydrogen atom bound to the ring. Most aryl groups are derived from benzene, the simplest aryl group is the phenyl group.
  • At least one aryl group is present in the sulfonium cation.
  • At least one mononuclear aryl group for example an aryl group with an aryl structure derived from benzene, such as phenyl or benzyl, is present.
  • At least one substitution is present on a mononuclear aromatic radical of the aryl group of the sulfonium-containing cation, that is, a hydrogen is replaced on the aromatic nucleus, for example by a functional group or an alkyl group.
  • the functional group can be present with or without a hetero atom such as oxygen, nitrogen, sulfur, phosphorus.
  • the belt accelerator is present as a mixture of at least two cationic belt accelerators, each of which has a different sulfonium cation.
  • the anions can be the same or different.
  • hexafluoro-antimonate is provided as the anion.
  • Mixing ratios of 1000 parts of the first belt accelerator to 1 part of the second belt accelerator up to equal proportions of the first and second belt accelerator are provided.
  • 100 parts of the first belt accelerator are mixed with 1 part of the second belt accelerator.
  • 10 parts of the first belt accelerator are mixed with 1 part of the second belt accelerator.
  • the belt accelerator regardless of whether it is present as a single compound or as a mixture, preferably has a melting point in the range from 145 ° C to 165 ° C, particularly preferably in the range from 155 ° C to 160 ° C.
  • a “solid insulation material” is particularly a composite of a carrier, a barrier material, a tape adhesive and the tape accelerator. Depending on the size and shape of the barrier material, a carrier is present or not. The carrier is therefore optional.
  • An electrically insulating material is used as the barrier material, in particular one that can be glued together in the form of particles to form a flat structure such as a tape, paper or the like.
  • Mica is particularly preferred in this context because mer also combines a particularly high dielectric strength with high temperature resistance.
  • all barrier materials that are suitable for storing the belt accelerator according to the invention and for producing an insulation system after casting, impregnation and curing can be used here.
  • the barrier material is preferably at least partially in the form of platelets.
  • a carrier in the form of woven material such as glass fiber cloth, non-woven material (“non-woven”) such as e.g.
  • Fleece in particular a polyester fleece, paper and / or film before.
  • the carrier can also be perforated in the form of a film.
  • The, preferably particulate, barrier material is located in the solid insulation material on, in and / or on this carrier.
  • the solid insulation material comprises a tape adhesive in the form of a thermoplastic polyvinyl acetal and / or a polyester, for example a liquid polyester.
  • the polyester comprises hydroxyl groups and / or carboxy groups as functional units.
  • Possible polyvinyl acetals are, for example, butyraldehyde and / or acetaldehyde.
  • the epoxy-containing tape adhesives show less good properties together with the tape accelerators according to the present invention than epoxy-group-free tape adhesives.
  • the tape adhesive is, for example, in the form of a blend, so that proportions of epoxy-containing compounds together with the thermoplastic polyvinyl acetals and / or the polyesters are present, it being preferred that the properties of the thermoplastic polyvinyl acetals and / or the polyester dominate in the mixture that forms the tape adhesive.
  • the tape adhesive connects the at least one carrier and the barrier material in the solid insulation material, the insulation system. It is contained in the solid insulation material in an amount in the range from 1 to 30% by weight, preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.
  • the belt accelerator is embedded in the solid insulation material, which is present, for example, in the form of a belt, hence the term "belt accelerator”. This can be done, for example, by applying a surface.
  • the belt accelerator is embedded in the solid insulation material with an area coverage of 0.1 to 5 g / m 2 . It is preferably stored with an area application of 0.25 to 2 g / m 2 and particularly preferably with an area application of 0.5 to 1.5 g / m 2.
  • the impregnation agent essentially comprises an impregnation resin, but can also contain other components components - for example to modify the processing and / or the properties of the molding material - such as hardeners, catalysts, thinners, additives, fillers, etc. include.
  • a suitable impregnating resin in the impregnating agent contains a cationically polymerizable monomer and / or oligomer.
  • a suitable impregnating resin contains one or more anhydride-free compound (s) with oxirane and / or epoxy groups. These compound (s) can be wholly or partly aromatic, aliphatic and / or cycloaliphatic.
  • mixtures of cycloaliphatic epoxy resins with aromatic glycidyl ether epoxy resins are suitable impregnating resins for the purposes of the present invention.
  • Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexa-carboxylate with an aromatic epoxy resin for example a bisphenol A and / or F-di-glycidyl ether.
  • a mixture of aliphatic and / or aromatic epoxy resin with at least one cyclo-aliphatic epoxy resin is used specified.
  • the mixing ratio of aliphatic and / or aromatic to cyclo-aliphatic epoxy resin can assume values in the range from 80:20 to 5:95 - each expressed as a percentage by weight.
  • Preferred mixing ratios are in the range from 50:50 to 10:90, and preferably in the range from 30:70 to 15:85.
  • the band accelerator of structure I is a band accelerator that is cationically effective.
  • the belt accelerator according to structure I is a white, crystalline solid at room temperature, the melting point of which can be determined by means of DSC. If the belt accelerator according to structure I changes and / or decomposes as a result of a temperature treatment, this would result in a lowering of the melting point.
  • Figures 4 and 5 show the results of the corresponding tests.
  • FIG. 4 shows a sample of the belt accelerator according to structure I at room temperature with a melting point of 160 ° C. known from the literature.
  • FIG. 5 shows the same sample after a temperature treatment of 168 hours at 70.degree. Melting point unchanged.
  • FIG. 6 again shows the same sample which, after the measurement that can be seen in FIG. 5, was subjected to a temperature treatment for a further 24 hours at 80.degree. Melting point still unchanged.
  • the tape accelerator according to structure I can withstand the temperature loads that occur during the production of a winding tape insulation and during the preparations for impregnation with impregnating agent, unchanged.
  • the compound withstands the temperature loads unchanged; on the other hand, an ionic compound composed of a sulfonium-containing cation with a hexafluoroantimonate anion, shown here using the example of the compound according to structure I, also retains its reactivity towards the Impregnation resin, such as the cycloaliphatic celloxide 2021P:
  • FIGS. 7 and 8 show a concentration of less than 1% by weight of belt accelerator in a typical impregnation resin, here a cycloaliphatic epoxy resin.
  • FIG. 7 shows the reactivity of the fresh strip accelerator and
  • FIG. 8 shows the reactivity in comparison therewith after a temperature treatment as in FIG. 6, i.e. the same strip accelerator after 168 hours of storage at 70 ° C and 24 hours at 80 ° C: also the reactivity, as before, the melting point of the compound used remains unchanged.
  • N- (p-methoxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate is also a white, crystalline solid when fresh, like the sulfonium hexafluoroantimonate tested in FIGS. 3 to 8.
  • FIG. 9 shows the DSC measurement for determining the melting point of the fresh N- (p-methoxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate. A peak at 116 ° C, which indicates the melting point, is clearly visible.
  • FIG. 10 shows the same sample after a temperature treatment of 48 hours at 70.degree. The spectrum has clearly changed, so the substance is no longer in its original state. A peak at 109 ° C proves the lowering of the melting point due to contamination.
  • FIG. 11 shows the same measurement of the same sample after a temperature treatment of 168H at 70.degree. It is clear that there is no longer any detectable melting point.
  • FIG. 12 shows sufficient reactivity of the system with the fresh N- (p-methoxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate
  • the comparison with the N- (p- Methoxybenzyl) -N, N-dimethylanilinium hexafluoroantimonate turns out to be considerably less favorable in terms of reactivity and - as Figure 13 shows, the curing reaction of the belt accelerator stored for 168 hours at 70 ° C is according to the prior art, the N- (p-methoxybenzyl) -N, N- dimethylanilinium hexafluoroantimonate greatly reduced.
  • Table 2 shows the viscosities of mixtures of commercially available epoxy resins at temperatures from 50 ° C to 70 ° C:
  • FIG. 14 shows the graphic representation of Table 2. The decreasing viscosity with increasing temperature can be clearly seen.
  • the cationic belt accelerator in accordance with a preferred embodiment of the present invention is referred to herein as "SI-150", a trade name under which the compound
  • the concentration of belt accelerator By varying the concentration of belt accelerator, the impregnation resin composition and the impregnation temperature, the reactivity and / or the gel time and the sensitivity to low belt accelerator concentrations can be controlled.
  • Tables 3 to 5 show the results of setting the gel time via the belt accelerator concentration and / or the impregnating resin composition and / or the temperature.
  • FIG. 15 shows the gel times of mixtures of EP162 and C2021P at 70 ° C. as a function of the concentration of SI-150.
  • the gel time increases with increasing content of tape accelerator, but also at a very low concentration of 0.1% A clear gelation can still be seen in the belt accelerator, so that even such low concentrations of the belt accelerator according to an exemplary embodiment of the invention are sufficient to achieve a stable insulation system.
  • FIG. 16 shows the gel times at the same concentration of belt accelerator, but at different temperatures and different mixing ratios in the impregnation resin.
  • FIG. 17 shows the gel times of mixtures of 20% EP162 and 80% C2021 with different concentrations of belt accelerator as a function of temperature.
  • the reactivity and / or sensitivity of the impregnating resin mixture with the belt accelerator mixture can be adjusted via the composition of the impregnation resin. It could be shown, completely surprisingly, that with an increasing proportion of cyclo-aliphatic epoxy resin in the impregnation resin composition, the reactivity of the belt accelerator SI-150 increases even at such low concentrations Belt accelerator such as 0.001% is still hardenable.
  • FIGS. 18 to 21 show the curing reactions with various blends in the impregnating resin at belt accelerator concentrations as low as 1%, 0.1%, 0.01% and finally 0.001% of belt accelerator. It can be clearly seen in the graph above that with increasing content of cycloaliphatic epoxy resin C2021P, complete curing also occurs significantly at a content of belt accelerator of 0.001.
  • Mixtures with a proportion of 70% or more of cyclo-aliphatic epoxy resin, such as, for example, the C2021P, are particularly suitable for as complete a curing as possible in the complete mica tape insulation.
  • the tape adhesive for example, connects the particles of the mica platelets to one another to form a tape that ideally shows storage stability for at least 3 months, better still for 6 months or longer.
  • Storage stability is understood to mean that, on the one hand, there is constancy in their processing behavior. These can - for example in the case of a belt - be checked via a change in its flexural strength.
  • Aromatic glycidyl ether epoxy resins for example bisphenol A diglycidyl ether or epoxidized novolaks, are conventionally used as mica tape tape adhesives.
  • these tape adhesives are only suitable to a limited extent. This can be traced back to the storage stability of the solid insulation materials formed accordingly. The storage stability can be seen by measuring the flexural rigidity.
  • a conventional solid insulation material that has been treated with a belt accelerator according to the invention for example the SI-150, in an area application of 1 g per meter, increases its flexural strength by more than 50% after just 4 weeks at 40 ° C.
  • the bending stiffness is a measure of the workability of the solid insulation material and is desirably as small as possible - for example for the production of a winding. In general, bending stiffnesses of more than 70 to 75 N per meter are seen as borderline for processing.
  • Table 8 shows the comparison of the two mica tapes Poroband 4037 from Isovolta, once with subsequent application of SI-150, once without.
  • tape adhesives without epoxy groups such as thermoplastic polyvinyl acetals, especially when acetalized with butyraldehyde and / or acetaldehyde) and / or liquid polyesters with hydroxy and / or carboxy groups, do not show any significant edges increase in flexural rigidity with the same aftertreatment with SI-150.
  • a mixture of the polyvinyl acetal Mowital® BA55HH from Kuraray and the carboxy-functional polyester polyol Rokrapol 7075 from Robert Kraemer can be used to formulate a tape adhesive that has properties comparable to conventional epoxy-containing tape adhesives, but in combination with SI-150 shows significantly better storage stability.
  • SAN-AID SI-150 shows only an increase in flexural rigidity of 14% after storage for 4 weeks at 40 ° C. The absolute value of 70-75 N / nr 2 is also not exceeded.
  • Table 9 shows the corresponding measurement results: Table 9:
  • a further measure of the storage stability of strip accelerator-containing mica strips is the constancy of the strip accelerator activity and / or reactivity.
  • FIG. 22 shows the hardening reaction of a mixture of 20% EP162 and 80% C2021P against a mica tape with a tape accelerator application of 1 g / nr 2 of SI-150, the mica tape sample not having been thermally post-treated.
  • FIG. 23 shows the hardening reaction of a mixture of 20% EP162 and 80% C2021P against a mica tape with a tape accelerator application of 1 g / nr 2 of SI-150, the mica tape sample being stored thermally at 40 ° C. for 4 weeks.
  • the range of the band accelerator out of the mica band can be shown in a simple experiment.
  • a mica tape sample measuring 400x25mm is wound onto a 4mm thick mandrel.
  • the resulting roll is removed from the mandrel and placed in front of the curvature of the bottom of a test tube using tweezers.
  • 4.4 g of preheated impregnation resin - e.g. 70 ° C - are added.
  • the impregnating resin slowly penetrates the roll, so that the curvature of the bottom and the gusset in the roll are also filled. A resin protrusion of ⁇ 10mm remains.
  • the roll prepared in this way is then subjected to the hardening program in the convection oven and then assessed for complete hardening, especially on the bottom, gusset and protrusion as well as the roll itself.
  • SAN-AID S1-150 shows with a mixture of 20% EP162 and 80% C2021 P as impregnation resin in this test a complete hardening of the roller and all resin areas.
  • Figure 24 shows the course of the temperature-dependent loss factor tan d of an insulation system from a mica tape sample according to an embodiment of the present invention with a tape accelerator application of 1g per meter, impregnated and soaked with an impregnating agent, a mixture of 20% EP162 and 80 % C2021P comprising after a final curing of 10 hours at 145 ° C.
  • the invention provides for the first time a solid insulation material with a tape accelerator and, optionally, a suitable tape adhesive, which can be quickly and completely treated with anhydride-free impregnating agent, even in areas with little tape accelerator, under the conditions of vacuum pressure, for example.
  • Impregnation -VPI - provides a stable insulation system with a low number of imperfections.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Insulating Bodies (AREA)
  • Organic Insulating Materials (AREA)

Abstract

L'invention concerne un accélérateur en bande et un matériau d'isolation solide renfermant cet accélérateur en bande, qui peut être utilisé pour produire un système d'isolation exempt d'anhydride pour moteurs et générateurs, en particulier sous la forme d'une isolation de bande d'emballage. En particulier, cette invention concerne un système d'isolation exempt d'anhydride pouvant être produit au moyen d'un procédé d'imprégnation sous vide et sous pression (VPI). Un tel système d'isolation comprend un matériau d'isolation solide permettant de produire le système d'isolation exempt d'anhydride, par imprégnation et enrobage au moyen d'un agent d'imprégnation, puis durcissement. Cette invention permet de fournir pour la première fois un matériau d'isolation solide renfermant un accélérateur en bande et éventuellement un ciment pour cordons adapté qui permet d'obtenir un système d'isolation stable de manière rapide et complète au moyen d'une imprégnation exempt d'anhydride, également dans des zones dépourvues d'accélérateurs en bande, dans des conditions d'imprégnation sous vide et sous pression.
EP20764002.0A 2019-09-04 2020-08-11 Accélérateur en bande et son utilisation, matériau d'isolation solide et système d'isolation exempt d'anhydride Pending EP4003954A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019213420 2019-09-04
PCT/EP2020/072445 WO2021043541A1 (fr) 2019-09-04 2020-08-11 Accélérateur en bande et son utilisation, matériau d'isolation solide et système d'isolation exempt d'anhydride

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EP4003954A1 true EP4003954A1 (fr) 2022-06-01

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US (1) US12129359B2 (fr)
EP (1) EP4003954A1 (fr)
CN (1) CN114599720B (fr)
WO (1) WO2021043541A1 (fr)

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* Cited by examiner, † Cited by third party
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SU878081A1 (ru) 1978-06-23 1983-12-15 Предприятие П/Я А-1430 Электроизол ционна лента и способ ее изготовлени
DE3824254A1 (de) 1988-07-14 1990-01-18 Siemens Ag Isolierband zur herstellung einer mit einer heisshaertenden epoxid-saeureanhydrid-mischung impraegnierten isolierhuelse fuer elektrische leiter
DE59000858D1 (de) 1989-01-16 1993-03-25 Ciba Geigy Ag Araliphatische sulfoniumsalze und deren verwendung.
JP2797025B2 (ja) 1989-10-31 1998-09-17 三新化学工業株式会社 ジアルキルスルホニウム化合物
EP0611796A1 (fr) 1993-02-18 1994-08-24 Ciba-Geigy Ag Masses à couler fortement chargées exemptes d'halogène
JP4403829B2 (ja) 2004-02-27 2010-01-27 株式会社日立製作所 回転電機，電気絶縁線輪及びそれに用いるエポキシ樹脂組成物
MXPA06014634A (es) 2004-06-16 2008-03-13 Isovolta Cinta de mica que tiene contenido maximizado de mica.
EP1754733A1 (fr) * 2005-07-26 2007-02-21 Huntsman Advanced Materials (Switzerland) GmbH Composition
EP2748224B1 (fr) 2011-09-09 2017-07-05 ABB Research Ltd. Procédé pour préparer une isolation électrique pour la haute tension
DE102015214872A1 (de) 2015-02-05 2016-08-11 Siemens Aktiengesellschaft Isolierband für eine Spule und Wickelband-Isoliersystem für elektrische Maschinen
DE102015204885A1 (de) 2015-03-18 2016-09-22 Siemens Aktiengesellschaft Isolationssystem, Verwendungen dazu, sowie elektrische Maschine
DE102015205328A1 (de) 2015-03-24 2016-09-29 Siemens Aktiengesellschaft Bandkleber für ein Isolierband in einem Isolationssystem und Isolationssystem
DE102015213815A1 (de) 2015-07-17 2017-01-19 Siemens Aktiengesellschaft Fester Isolationswerkstoff, Verwendung dazu und damit hergestelltes Isolationssystem
DE102015213535A1 (de) 2015-07-17 2017-01-19 Siemens Aktiengesellschaft Fester Isolationswerkstoff, Verwendung dazu und damit hergestelltes Isolationssystem
DE102015213537A1 (de) 2015-07-17 2017-01-19 Siemens Aktiengesellschaft Fester, insbesondere bandförmiger, Isolationswerkstoff, Formulierung für ein Imprägniermittel zur Herstellung eines Isolationssystems in einem Vakuumimprägnierverfahren damit und Maschinen mit derartigem Isolationssystem
EP3341428A4 (fr) 2015-08-27 2019-04-17 Toray Industries, Inc. Compositions de résine époxy, et matériaux composites renforcés de fibres préparés à partir desdites compositions
KR20180059824A (ko) 2015-09-28 2018-06-05 도레이 카부시키가이샤 경화 속도가 변화하는 수지 조성물을 구비한 프리프레그
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RU2019114198A (ru) * 2016-10-21 2020-11-24 Торэй Индастриз, Инк. Композиции эпоксидных смол и армированные волокном композитные материалы, полученные из них

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US12129359B2 (en) 2024-10-29
CN114599720B (zh) 2025-03-28
CN114599720A (zh) 2022-06-07
US20220235199A1 (en) 2022-07-28
WO2021043541A1 (fr) 2021-03-11

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